A new empirical rate equation for adsorption kinetics at solid/solution interface

It has been shown that most of the previously reported empirical rate equations for kinetics of adsorption at the solid/solution interface show high relative errors at the initial times of adsorption. In the present work we made a modification onto pseudo-first-order and pseudo-second-order models and presented a new empirical rate equation, called the modified pseudo-n-order (MPnO) model. The results of fitting to the experimental data show that the MPnO model has low relative errors in the whole range of adsorption time.     

A numeric model for the kinetics of water vapor sorption on cellulosic reinforcement fibers

Some natural fibers like flax, hemp and others show excellent mechanical properties that make them a promising choice for the reinforcement of polymers. The increasing research on natural fiber reinforced composites has still left important questions open, mainly concerning the fiber–matrix interface. Compared to the well optimized glass fibers, cellulose fibers show very different interaction with matrix polymers and adhesion promoters. The hydrophilic cellulose structure allows for the penetration of a considerable amount of water into the amorphous regions of the fibers, eventually exceeding 20% by mass, depending on fiber type, preparation and environmental humidity. Even embedded in totally apolar polymers the cellulose partly retains its ability for water sorption, which results in unfavorable effects, such as dimensional changes, decrease in strength, roughening of the surface, etc. The interaction of differently prepared fibers with water vapor and the effect of surface treatment is investigated by measuring the dynamics of water vapor sorption. An exponential model is used for the numerical evaluation of the sorption and desorption kinetics. The model not only allows for an excellent fit of the experimental isotherms, but without any further assumptions it immediately gives evidence of the existence of two distinct mechanisms for the exchange of water vapor, related to different sorption sites. These specific mechanisms are represented by individual sorption–desorption isotherms as components of the total isotherms. The model provides a clearer differentiation of the effects of fiber preparation and modification with respect to interfacial interactions.     

The interaction effects between adsorbed molecules in the Statistical Rate Theory approach to the kinetics of mixed-gas adsorption

Kinetics of adsorption of single gases and their binary mixture on an energetically homogeneous surface are studied theoretically using the Statistical Rate Theory (SRT) of interfacial transport. Additionally, the influence of intermolecular interactions on the rate of adsorption is modeled using the Regular Adsorbed Solution Theory. The theoretical results are classified and assigned to different types of experimental conditions under which the changes of the adsorbate concentration near the adsorbing surface are considerable or they are negligible. Predictions of the theory are verified using adsorption data measured in real systems.     

Application of the Statistical Rate Theory of interfacial transport to investigate the kinetics of mixed-gas adsorption onto the energetically homogeneous and strongly heterogeneous surfaces

Kinetics of mixed-gas adsorption by using the Statistical Rate Theory is studied. Applying the adsorption lattice model two cases are investigated: when adsorption occurs like on the homogeneous surface and when energetic heterogeneity of adsorption system can be described by the rectangular adsorption energy distribution function. The model of calculations offers possibility of theoretical prediction of the rate of adsorption/desorption of mixture components by using the single-gas equilibrium and kinetic data. Possible changes of adsorbate concentration near the adsorbing surface are also taken into account. The obtained theoretical expressions were verified using real adsorption systems.     

Second order time evolution of the multigroup diffusion and P1 equations for radiation transport

An existing solution method for solving the multigroup radiation equations, linear multifrequency-grey acceleration, is here extended to be second order in time. This method works for simple diffusion and for flux-limited diffusion, with or without material conduction. A new method is developed that does not require the solution of an averaged grey transport equation. It is effective solving both the diffusion and P₁ forms of the transport equation. Two dimensional, multi-material test problems are used to compare the solution methods.     

A novel approach for the quantitative kinetic study of reactions at solid/liquid interfaces in the presence of power ultrasound

A novel cell and procedure is described which permits the quantitative mechanistic study of ultrasonically enhanced reactions which occur at solid/liquid interfaces. A model of a controlled and calculable time-average rate of mass transport to and from the interface is used in order to compare experimental results with theoretical predictions based on mechanistic reaction schemes. In this way concentrations of mechanistically significant species near the interface can be related to those in bulk solution and hence the sonochemical effects of ultrasound dissected from those arising purely from mass transport. The effect of ultrasound is demonstrated for the reaction dissolution of p-chloranil in the presence of aqueous base and for the reaction of the same substrate with the aromatic amine, N,N-dimethyl-phenylenediamine, both systems which have been studied previously in the absence of ultrasound. Complementary atomic force microscopy images are also reported.     

Effective impedance model for analysis of reflection at the interfaces of photonic crystals

We present an alternative definition of impedance to describe the reflection at the interfaces of photonic crystals. We show that this effective impedance can be defined only by the properties of the photonic crystal modes and is independent of the properties of the incident region. This approximate model successfully explains the main features in the reflection spectrum and of various interface terminations of photonic crystals. In particular, we show an impedance matching condition at which reflectionless transmission of power to a low-group-velocity photonic crystal mode is possible, a property that is attractive for various dispersion-based applications of photonic crystals.     

The influence of a small amount of active sites on the adsorption kinetics of nitrogen on ruthenium

Recently, Dahl et al. [S. Dahl, A. Logadottir, R.C. Egeberg, J.H. Larsen, I. Chorkendorff, E. Törnqvist, J.K. Nørskov, Phys. Rev. Lett. 83 (1999) 1814; S. Dahl, E. Törnqvist, I. Chorkendorff, J. Catal. 192 (2000) 381] have proposed very interesting hypothesis that the rate of dissociation and adsorption of nitrogen on Ru(0 0 0 1) facet is totally dominated by the presence of a small amount of step sites on Ru(0 0 0 1) terraces. Following this idea, a kinetic model, based on applying the Statistical Rate Theory approach, was developed in order to explain if such mechanism is able to explain the observed features of the system N₂/Ru(0 0 0 1). As a result, it was stated that the activation barrier for adsorption on the active (step) sites is equal to 36 kJ/mol; in turn, the adsorption energy of nitrogen atoms on the active sites is 43 kJ/mol. It implies that the rate of adsorption via the active sites is much faster than direct adsorption on the three-fold hollow sites; moreover, the occupation of the active sites is always close to zero at the investigated temperatures, so they are not blocked and may act as an indirect channel for adsorption. Thus, the rate of nitrogen adsorption on Ru(0 0 0 1) surface is governed by the rate of diffusion of nitrogen atoms from the active sites into the three-fold hollow sites. The analysis of thermodesorption spectra revealed an important role of repulsive interactions between the N atoms adsorbed on the hollow sites, the associated interaction parameter between nearest neighbors was estimated to be 5 kJ/mol. The presence of small amount of gold on Ru(0 0 0 1), apart of blocking the active sites, seems to remove the repulsion between nitrogen atoms.     

扩散理论对RLA模型中交换作用的研究

以扩散理论为基础，建立以“基本微观过程” 为核心的新模型，引入交换比的概念，对存在表面活化剂时薄膜生长的微观过程进行Kinetic Monte Carlo模拟.模拟发现，活化层原子和沉积原子都会发生跨层间的扩散，跨层扩散主要是单个原子的扩散，层间扩散的原子数目随着温度的升高或沉积厚度的增加而增多.RLA模型中的“交换作用”只是若干个“基本微观过程”的组合，大多数交换不是位置的“完全交换”，交换比也并非恒为1.     

扩散理论对RLA模型中交换作用的研究

以扩散理论为基础,建立以“基本微观过程” 为核心的新模型,引入交换比的概念,对存在表面活化剂时薄膜生长的微观过程进行Kinetic Monte Carlo模拟.模拟发现,活化层原子和沉积原子都会发生跨层间的扩散,跨层扩散主要是单个原子的扩散,层间扩散的原子数目随着温度的升高或沉积厚度的增加而增多.RLA模型中的“交换作用”只是若干个“基本微观过程”的组合,大多数交换不是位置的“完全交换”,交换比也并非恒为1. 关键词： 扩散理论 薄膜生长 交换作用 RLA     

Nanocrystallization of CaCO3 at solid/liquid interfaces in magnetic field: A quantum approach

With the application of 1.2 T external magnetic field, 90% of CaCO₃ soluble molecules in water flow precipitate on stainless steel 316 solid/liquid interface in the form of aragonite/vaterite. The magnetic field increases locally the thermodynamic potentials at interface, favoring the formation of aragonite than calcite, despite the fact that the field-free ground electronic state of aragonite is situated higher than of calcite. A quantum mechanical model predicts that magnetic fluctuations inside the liquid can be amplified by exchanging energy with an external magnetic field through the angular momentum of the water molecular rotors and with the macroscopic angular momentum of the turbulent flow. The theoretical model predicts that the gain is higher when the magnetic field is in resonance with the rotational frequencies of the molecular rotors or/and the low frequencies of the turbulent flow and that aragonite concentration is increasing at 0.4 T in agreement with the experimental results. Contrary to calcite, aragonite binds weakly on flow surfaces; and hence the process has significant industrial, environmental and biological impact.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Studies of adsorption equilibria and kinetics in the systems: Aqueous solution of dyes-mesoporous carbons

Two carbonaceous materials were synthesized by using the method of impregnation of mesoporous silicas obtained by applying the Pluronic copolymers as pore-creating agents. The isotherms of adsorption of methylene blue and methyl orange from aqueous solutions were measured by the static method. The profiles of adsorbate concentration change in time were obtained from the UV-vis spectra. The adsorption isotherms and kinetic dependence were discussed in the terms of theory of adsorption on heterogeneous surfaces.     

Equilibrium statistics of the one-dimensional Ising model for a solid solution of limited size

We treat the one-dimensional Ising model of a binary solution closed in a ring. We analyze the criteria for two-phase behavior of the model system. Bimodality of the distribution function of the atoms over clusters was used as one of the criteria. The effect of the size and dimensionality of the model on the form of the thermodynamic functions is traced. It is shown that in the one-dimensional Ising model of limited size there is a configurational change which can be treated as a smeared phase transition. The results of the present work obtained for a small one-dimensional model agree well with the results for two-dimensional small systems and are analogous to the behavior of three-dimensional systems. Khakassk State University. Tomsk State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 3–8, January, 1997.     

A four-channel unitary model for the description of heavy-ion collisions at relativistic energies

We expand a previously formulated model for nuclear abrasion in ion-ion collisions where now nucleons in both projectile and target can be excited. Describing the state of excitation by an effective channel we rigorously impose unitarity and compare the results with those of a heuristic treatment of unitarity by Hüfner, Schäfer and Schürmann. We find corrections to the latter theory which grow up to a factor of two with the number of abraded nucleons.     

Origin of the defect states at ZnS/Si interfaces

Electrical characterisation of silicon surfaces contaminated by a zinc-sulphide overlayer has been carried out by forming Schottky diodes on the silicon after the ZnS has been etched off. The techniques include current-voltage, capacitance-voltage, and deep-level transieni spectroscopy. The Schottky diodes show clear memory of the presence of the ZnS overlayer and the electrical characteristics are far from ideal. Five deep levels in the sub-surface region of the silicon are detected, corresponding to the Zn⁺, Zn⁺⁺, S^–, S^–– states and probably to a Zn–B complex (p-type). Diffusion of the zinc and sulphur into the silicon is therefore confirmed and this diffusion is thought to create a compensated layer at the interface. These impurity states control the electrical characteristics of the surface in these diodes.     

Ultrasoft X-ray spectroscopy with variation of the electron excitation energy as a method for analyzing thin films and solid/solid interfaces

The application of ultrasoft X-ray spectroscopy with variation of the electron excitation energy for phase analysis of thin films and phase reactions at solid/solid interfaces is considered. CN _x nanocondensatess obtained by pulsed arc sputtering of graphite in the presence of nitrogen, silicon implanted with hydrogen ions, and Fe-Co silicides fabricated by ion-beam synthesis have been studied.